Cyclohexene phosphonates and their preparation



Patented Apr. 24,1951 7) CYOLOHEXENE PHOSPHONATES AND THEIR PREPARATION I Joseph B. Dickey, Harry W. Coover,Jr., and Newton H. Shearer, Jr., Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y.,

' a corporation of New Jersey i M 'No Drawing. Application July 9, 1949,

Serial No. 103,952

11 Claims. (C 1. 260-461) This invention relates to the preparation of, 'cyclohexene phosphonates by the reaction of butadiene or substituted butadienes with vinyl :phosphonates or substituted vinyl phosphonates and the products resulting therefrom.

Esters of phosphorus-containing acids have;

become of decided interest lately in various connections, particularly for insecticidal or fungicidal purposes. Also, the esters of phosphoruscontaining acids have shown themselves to be useful as plasticizers for cellulose esters and for certain types of vinylpolymers.

An object of our invention is to provide a new ype of esters of phosphorus-containing acids. Another objectof our invention is to provide esters of phosphorus-containing acids, the acid radical of which contains a ring structure therein. A further object of our invention is to provide a method of making phosphorus-containing esters in which butadiene is employed as the starting material.

A still further object of our invention is to provide novel chemical compounds which are useful for plasticizing polymeric materials and for insecticidal or fungicidal purposes. Other objects of our invention will appear herein.

We have found that cyclohexene phosphonates can be readily prepared by the reaction of a conjugated diene, such as butadiene or a substituted butadiene, with a vinyl phosphonate or a substituted vinyl hosphonate. The reaction which occurs is as follows:/ Y0H=0XP0K0R 2 -oz'z=ojz"o z=o Z;

I t Z Z PO(OR)2 The compounds comprising this invention are represented by the formula of the finished product in the above equation wherein Y is a hydrogen atom, a carbalkoxy group or a nitrile group; X is hydrogen or alkyl; R is alkyl; and Z is hydrogen or alkyl. pounds is carried out by heating together the reactants such as at a temperature within the range of 100-250 C. for a time within the range of, 1 10;, hours, 7 After the reaction has occurred,

The preparation of these comy the *cyclohexene phosphonates formed are iso lated therefrom by distillation under reduced pressure; l

Theconjugated dienes which may be employed as reactants may be butadie'ne, or it may be a sub- 'stituted' butadiene. In addition to butadiene some of the compounds which are connection are the following:

has

useful in this t -l lwl l gm n In the above formulas the alcohol groups may be any alkyls up to 18 carbon atoms, but the compounds which are most readily available and the easiest to work with contain only alkyl groups of 1-4 carbon atoms, particularly methyl and ethyl. Therefore, usually" it is desirable in preparing cyclohexene' phosphonates to use either butadiene or a dimethyl or diethyl butadiene .unless a compound of some particular structure is desired.

The vinyl or substituted vinyl phosphonates which may be employed as the starting material in reactions in accordance with our invention correspond with the formula I YCH=CXPO(OR) 2 Y may be either a hydrogen atom, a carb'alko'xy group such as carbomethoxy or carboethoxy or a nitrile group such as CN; X may be either hydrogen or alkyl; whereas R in each instancehis an alkyl group. Although in these compou'ndsit ,is preferred that the alkyl groups bejof. 1-4: carbon atoms, here again the alkyl groups may have any number of carbon atoms up to 18. When these two reactants are heated together as described herein, ring formation occurs and the resulting products obtained arecyclohexene phosphonate esters, the substituents being arranged around 3 the ring as shown in the type reaction given herein.

The compounds prepared in accordance with our invention exhibit insecticidal and/ or fungicidal properties and, therefore, are useful in circumstances wherein those properties are desired. Also, these compounds when mixed with cellulose esters or vinyl acetate or similar polymers exhibit a plasticizing action making those polyinersniore readily workable. The cyclohexene phosphonates prepared in accordance with our invention caiibe mixed with inert powder such as powdered diato' maceous earth or finely divided sulfur'and can-be employed as a dust to protect plant life against harmful insect pests. If desired, instead-oiapply-- ing in the form of a dust the cyclohexen -phosphonate can be dissolved in a like petroleum. distillate and employed inemulsion formfor insecti: cida1 purposes. v

' The following examples illustrate the preparation of cyclohexene phosphonates in accordance with our invention:

Example 1.-5-carbometh0:ny-4-diethyl phosphonato cyclohexene.l5 parts of butadiene, 0.2 part of hydroquinone and '7 parts of diethylp carbomethoxy vinyl phosphonate were dissolved in 50 parts of absolute ethyl alcohol and the mass was heated in a sealed container at 100 C. for hours. Awhite, polymeric material formed which was separated "from the mass by filtration. The filtrate was fractionally distilled and the product being collected at 115- 118 C. at 1 mm. pressure. A yield of 70% of 5-carbomethoxy-4-diethyl phosphonato cyclohexene was obtained} Example 2.4-diethyl phosphonato-4-methyl cyclohexene.12 parts of butadiene, 0.2 part of hydroquinone and 9lparts of diethyl isopropenyl phosphonate were dissolved in parts of abso lute ethyl alcohol and. the solution was heated in a closed container .at 200 C. for '7 hours. The mass was then subjected to fractional distillation at reduced pressure whereby the abovenamed product was obtained in good quantity.

Example 3.4-diethyl phosphonato cyclohescene.10 parts of butadiene, 0.2 part of hydroquinone and 7 parts'of diethyl vinyl phosphonate were placed in an autoclave and heated at 150. C. -;for 5 hours. The resulting material was subv.j'ected to fractional distillation and a considerable amount of the above-named product was .obtained. In the above examples other compounds which :have been mentioned as suitable. in this reaction ::may be substituted in commensurate quantities fin the above examplesto obtain the ldesired p'roducts. For instance, instead of butadiene, 2 ,3- dirnethyl butadiene or any of the other conjugated dienes specified herein may be employed, the compounds used as starting materiais'being governed by the products which are desired, the compounds to be used being determined by reference to the general equation which has been given in this specification.

We claim: 7 l. A method for preparing cy'elohexene phosphonates which comprises heating together at loo-250 C. for 1-10 hours a compound having the formula CZ2=CZ- -CZ=CZ2, 12 being selected from hydrogen and alkyl with a compound having the formula 4 R being alkyl, X being selected from the group of hydrogen and alkyl and Y being selected from the group of hydrogen, carbalkoxy and nitrile.

2. A method for preparing cyclohexe'ne phosphonates which comprises heating together at IOU-250 C. for 1-10 hours butadiene and a compound having the formula x i 3503:0- OR R: being alkyl, being selected from the group of hydrogen and alkyl and Y being selected from the group ofhydrogen, carbalkoxy and nitrile.

3. A method for preparing cyclohexene phosphonates which comprises heating together at IOU-250 C. for 1-10 l'i'ours a compound having the formula.CZz=CZ-CZ=CZz, Z being selected from the .group of hydrogen and alkyl and diethyl vinyl phosphonate.

4. A method for preparing cyclohexene phosphonates which comprises heating together at 100-250 C. for 1-10 hours butadiene and diethyl vinyl phosphonate. 5. A methodfor preparing cyclohexene phosphonates which comprises heating together at LOG-250 C. for l-lO hours butadiene and diethyl isopropenylphosphonate.

6. A method for preparing cyclohexene phosphonates which comprises heating together at lilo-250 C. for l-lOhours butadiene and diethyle-carbomethoxy-vinyl phosphonate.

5 '7. A compound having the formula X and Z being selected fromthe group of hydrogen and alkyl, R being al-kyl and Y being selected from the group of hydrogen, carbalkcxy .and nitrile.

8. A compound having the formula X and ,Zbeing selected from the group of hydrogen and ,alkyl and Y being selected from the group of hydrogen, carbalkoxy and nitrile.

9. Diethyl phosphonato cyclohexene. 10. Diethyl phosphonato-methyl cyclohexene. 11. Diethyl phosphonato-carbomethoxy cyclohexene.

JOSEPH B. DICKEY. HARRY W. COOVER, JR. NEWTON H. SHEARE-R, JR.

Number 

1. A METHOD FOR PREPARING CYCLOHEXENE PHOSPHONATES WHICH COMPRISES HEATING TOGETHER AT 100-250* C. FOR 1-10 HOURS A COMPOUND HAVING THE FORMULA CZ2=CZ-CZ=CZ2, Z BEING SELECTED FROM HYDROGEN AND ALKYL WITH A COMPOUND HAVING THE FORMULA 